EP0650967B1 - Procédé de préparation d'alkylaluminoxanes sur support inerte - Google Patents

Procédé de préparation d'alkylaluminoxanes sur support inerte Download PDF

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Publication number
EP0650967B1
EP0650967B1 EP94113747A EP94113747A EP0650967B1 EP 0650967 B1 EP0650967 B1 EP 0650967B1 EP 94113747 A EP94113747 A EP 94113747A EP 94113747 A EP94113747 A EP 94113747A EP 0650967 B1 EP0650967 B1 EP 0650967B1
Authority
EP
European Patent Office
Prior art keywords
alkylaluminoxanes
process according
water
aluminum
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94113747A
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German (de)
English (en)
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EP0650967A1 (fr
Inventor
Stefan Dr. Gürtzgen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CROMPTON GMBH;CK WITCO GMBH
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Witco GmbH
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06Aluminium compounds
    • C07F5/061Aluminium compounds with C-aluminium linkage
    • C07F5/066Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C07F5/068Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • B01J19/2455Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/246Stationary reactors without moving elements inside provoking a loop type movement of the reactants internally, i.e. the mixture circulating inside the vessel such that the upward stream is separated physically from the downward stream(s)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • Alkylaluminoxanes especially methylaluminoxane, win increasingly important as an essential component of a new generation of catalyst systems for manufacturing of polyolefins ("Single Site Catalysts").
  • These new ones Catalysts consist essentially, as already made of classic Ziegler-Natta catalysis known from a transition metal compound as a catalyst and the beginning mentioned alkylaluminoxane as an organoaluminum cocatalyst component.
  • a transition metal compound preferably cyclopentadienedienyl, indenyl or fluorenyl derivatives Group IVa of the Periodic Table of the Elements.
  • alkylaluminoxane required in relation to the transition metal component
  • alkylaluminoxane to inert support materials, preferably SiO 2 (JCW Chien, D. He, J. Polym. Science Part A, Polym. Chem ., Vol. 29, 1603-1607 (1991).
  • Such supported materials also have the advantage of being easy to separate in condensed phase polymerizations (production of high-purity polymers) or of being usable as free-flowing powders in modern gas-phase processes, the grain morphology of the polymer
  • fixed alkylaluminoxanes as dry powders are physically more stable than solutions with a comparable Al content, especially for methylaluminoxane, which, as already mentioned, tends to gel in a toluene solution after a certain storage time .
  • EP 0 369 675 (Exxon Chemical) describes a process in which the immobilization of alkylaluminoxanes by reacting an approximately 10% solution of trialkylaluminum in heptane with hydrated silica (8.7 wt .-% H 2 O) is reached.
  • Immobilization is described in EP 0 442 725 (Mitsui Petrochemical) by reacting a toluene / water emulsion with an approx. 7% solution of trialkylaluminum in toluene in Presence of silica at temperatures from -50 ° C to +80 ° C causes.
  • the object of the present invention was therefore to achieve this To overcome disadvantages of the prior art and one To provide methods by means of which alkylaluminoxanes in high yield and homogeneity in a reproducible way can be fixed on inert carrier materials, wherein the degrees of loading can be varied within wide limits, the grain morphology of the carrier is retained and the products are ultimately available as free-flowing powders.
  • the invention relates to a method for producing of alkylaluminoxanes immobilized on inert carrier materials, which is characterized in that to Solutions of alkyl aluminum compounds in hydrocarbons water is dosed in a static mixer and the resulting in the form of dispersions, that is, lyophilic dispersions in the sol state, (cf. Römpp Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, New York 1990, p. 2299 ff) on inert Carrier materials are fixed.
  • Another object of the invention are on carrier materials fixed aluminoxanes, prepared according to the invention Method.
  • the dispersions used according to the invention can be produced by conventional hydrolysis processes of alkyl aluminum compounds in hydrocarbons as solvents.
  • the molar ratio of water to alkyl aluminum compounds is in the range from 0.8: 1 to 1.3: 1, preferably 0.9: 1 to 1.2: 1.
  • a method of production is preferred at which water to a solution of trialkyl aluminum in an aliphatic, cycloaliphatic or preferably aromatic hydrocarbon through a mixing nozzle into a static mixer, preferably one Beam loop reactor (SSR), is dosed (European patent application No. 93118245.5).
  • SSR Beam loop reactor
  • In the method according to the invention is in a volume flow ratio from 1: 2,000 to 1: 40,000, preferably 5000 - 20000, water into the jet loop reactor via the mixing nozzle dosed.
  • the jet loop reactor ensures because of the high circulation flow for a good and extremely fast mixing of the solution containing aluminum alkyl with water. Due to the high primary dispersion can be a locally too high concentration of water can be avoided, which otherwise lead to loss of yield due to the formation of aluminum hydroxide on the one hand and an undesirably high proportion of unconverted Aluminum trialkyl on the other hand, leads.
  • the average degree of oligomerization n which is expressed in the average molecular weight of the reaction product, can be influenced in a targeted manner by suitable metering of the reactants and control of the reaction parameters.
  • the molar ratio of H 2 O / aluminum trialkyl, in particular also in the case of trimethyl aluminum (TMA), can be set to the desired value. This is of particular importance since the activity of aluminoxanes as cocatalyst in olefin polymerization apparently depends on the degree of oligomerization of the aluminoxane used (Lit.:.W. Kaminsky, Nachr. Chem. Tech. Lab. 29, 373-7 (1981); W. Kaminsky et al., Makromol. Chem., Macromol. Symp. 3, 377-87 (1986)).
  • Trialkylaluminum compounds are preferred according to the invention with short-chain alkyl radicals, especially methyl radicals.
  • the carrier materials which can be used according to the invention are the porous oxides of one or more of the elements of groups II, III or IV of the periodic table, such as ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, preferably Al 2 O 3 and MgO and in particular SiO 2 , used.
  • These carrier materials can have grain sizes in the range from 1 to 300 ⁇ m, preferably 10 to 200 ⁇ m; Surfaces of 10-1000 m 2 / g, in particular 100-500 m 2 / g; N 2 pore volumes of 0.5-3 cm 3 , preferably 1-2 cm 3 .
  • the water content of the carrier materials should be ⁇ 5% by weight, preferably ⁇ 3% by weight and in particular ⁇ 1% by weight. in the If necessary, the commercially available carrier materials therefore before use at temperatures of 150 - 1000 ° C, preferably 200 - 500 ° C, 2 - 20 hours, if necessary at reduced pressure, dried.
  • the application and fixation of the aluminoxanes to the carrier materials takes place according to known methods either by continuous or portionwise addition of the carrier material to the submitted dispersions under simultaneous homogenization of the mixture, or by Synthesis of the dispersions directly in the presence of the carrier. These mixtures then become the solvent, if appropriate under reduced pressure.
  • the original grain morphology of the carrier material is not changed by this procedure.
  • the ratio of carrier to aluminoxane is relative within further limits can be varied, according to the invention it is so chosen that on the resulting free-flowing powder from carrier material and aluminoxane 5-40% by weight, preferably 10 - 25 wt .-% aluminum, in the form of aluminoxanes are available (see examples).
  • the method according to the invention enables production of supported aluminoxanes with almost quantitative yields of immobilized aluminum, based on the used Trialkylaluminium compounds without technically complex Procedural steps. Due to specifically adjustable Show parameters and reproducible process conditions these supported with the inventive method Alkylaluminoxanes, especially methylaluminoxane, high activities as cocatalysts and are therefore excellently suited for the further production of Catalyst systems for olefin polymerization.
  • a dispersion made with the jet loop reactor from 2.92 kg trimethylaluminum (TMA) (aluminum content: 36.8%), 0.58 kg water and 21.5 kg toluene (ratio H 2 O / TMA 0.8) was in a 40 1 steel reactor with 2.0 kg of silica support material (surface (N 2 -BET): 316 m 2 / g; N 2 pore volume: 1.55 ml / g; particle size distribution: 20 - 80 ⁇ m; residual water content: 2 , 6%) stirred and concentrated to dryness under vacuum at room temperature.
  • TMA trimethylaluminum
  • ratio H 2 O / TMA 0.8

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (8)

  1. Procédé pour la fabrication d'alkylaluminoxanes immobilisés sur des matériaux de support inertes, caractérisé en ce que l'on ajoute de l'eau de manière dosée à des solutions de composés alkylaluminium dans des hydrocarbures, et en ce que les alkylaluminoxanes résultants, présents sous forme de dispersions, sont fixés sur des matériaux de support inertes.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise des dispersions de méthylaluminoxanes dans des hydrocarbures aromatiques.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'eau et les composés alkylaluminium sont mis en oeuvre dans des rapports molaires de 0,8 - 1,3, de préférence de 0,9 - 1,2.
  4. Procédé selon la revendication 1, caractérisé en ce que l'on utilise comme matériau de support du SiO2 d'une teneur en eau < 5, de préférence < 3% en poids.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce que 5 - 40, de préférence 10 - 25% en poids d'aluminium est fixé sur le matériau de support sous la forme d'aluminoxanes.
  6. Procédé selon les revendications 1 à 5, caractérisé en ce que le matériau de support est ajouté de manière dosée à la dispersion.
  7. Procédé selon les revendications 1 à 5, caractérisé en ce que le matériau de support est déjà présent dans le mélange pendant la préparation de la dispersion.
  8. Cocatalyseur, consistant en alkylaluminoxanes immobilisés sur des matériaux de support inertes, fabriqué selon l'un quelconque des procédés conformément aux revendications 1 à 7.
EP94113747A 1993-10-27 1994-09-02 Procédé de préparation d'alkylaluminoxanes sur support inerte Expired - Lifetime EP0650967B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4336659A DE4336659A1 (de) 1993-10-27 1993-10-27 Verfahren zur Herstellung von Alkylaluminoxanen auf inerten Trägermaterialien
DE4336659 1993-10-27

Publications (2)

Publication Number Publication Date
EP0650967A1 EP0650967A1 (fr) 1995-05-03
EP0650967B1 true EP0650967B1 (fr) 1998-11-18

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EP94113747A Expired - Lifetime EP0650967B1 (fr) 1993-10-27 1994-09-02 Procédé de préparation d'alkylaluminoxanes sur support inerte

Country Status (7)

Country Link
US (1) US5446001A (fr)
EP (1) EP0650967B1 (fr)
JP (1) JPH07188253A (fr)
CA (1) CA2127671C (fr)
DE (2) DE4336659A1 (fr)
FI (1) FI115398B (fr)
NO (1) NO304692B1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6781007B2 (en) 2001-12-11 2004-08-24 Crompton Gmbh Process for preparing partial hydrolysates of organometallic compounds or transition metal catalysts immobilized on inert support materials

Families Citing this family (14)

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Publication number Priority date Publication date Assignee Title
TW454020B (en) * 1994-08-09 2001-09-11 Mitsui Chemicals Inc Olefin polymerization catalyst
MX9703592A (es) * 1994-11-17 1997-08-30 Dow Chemical Co Componente de catalizador soportado, catalizador soportado, su preparacion y proceso de polimerizacion por adicion.
US6043180A (en) * 1994-11-17 2000-03-28 The Dow Chemical Company Supported catalyst component, supported catalyst, their preparation, and addition polymerization process
US7153909B2 (en) * 1994-11-17 2006-12-26 Dow Global Technologies Inc. High density ethylene homopolymers and blend compositions
CA2163681C (fr) * 1995-11-24 2007-02-13 Daryll G. Harrison Catalyseur a base de monocyclopentadienylzirconium
EP0796859B1 (fr) * 1996-03-19 2002-07-31 Crompton GmbH Formulations homogènes et stables de composés organométalliques sensibles à l'oxydation dans des paraffines et procédé de leur préparation
US5990035A (en) * 1997-10-21 1999-11-23 Koeppl; Alexander Polymerization catalyst systems, their preparation, and use
US7220804B1 (en) 2000-10-13 2007-05-22 Univation Technologies, Llc Method for preparing a catalyst system and its use in a polymerization process
DE10348624A1 (de) * 2003-10-15 2005-05-25 Basell Polyolefine Gmbh Geträgerte Metallalkylverbindung und Verfahren zu deren Herstellung
EP1805226A1 (fr) 2004-10-29 2007-07-11 Exxonmobil Chemical Patents Inc. Compose catalytique contenant un ligand tridente divalent
WO2010144130A1 (fr) * 2009-06-11 2010-12-16 W.R. Grace & Co. -Conn. Procédé de fabrication d'un aluminoxane et catalyseurs comprenant l'aluminoxane ainsi préparé
WO2011078923A1 (fr) 2009-12-23 2011-06-30 Univation Technologies, Llc Procédés pour produire des systèmes de catalyseur
JP2013166876A (ja) * 2012-02-16 2013-08-29 Mitsui Chemicals Inc オレフィン重合用触媒、シート状オレフィン系重合体およびその製造方法、ならびに該シート状オレフィン系重合体を含んでなる成形体
US9650453B2 (en) * 2012-12-28 2017-05-16 Univation Technologies, Llc Methods of integrating aluminoxane production into catalyst production

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EP0578838A1 (fr) * 1992-04-29 1994-01-19 Hoechst Aktiengesellschaft Catalysateur de polymérisation d'oléfines, procédé pour sa préparation et son utilisation

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JPH0742301B2 (ja) * 1987-02-14 1995-05-10 三井石油化学工業株式会社 微粒子状アルミノオキサン、その製法およびその用途
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Publication number Priority date Publication date Assignee Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6781007B2 (en) 2001-12-11 2004-08-24 Crompton Gmbh Process for preparing partial hydrolysates of organometallic compounds or transition metal catalysts immobilized on inert support materials

Also Published As

Publication number Publication date
FI945043A0 (fi) 1994-10-26
EP0650967A1 (fr) 1995-05-03
CA2127671C (fr) 1999-03-16
NO944054D0 (no) 1994-10-25
FI945043A (fi) 1995-04-28
US5446001A (en) 1995-08-29
CA2127671A1 (fr) 1995-04-28
DE4336659A1 (de) 1995-05-04
JPH07188253A (ja) 1995-07-25
NO944054L (no) 1995-04-28
NO304692B1 (no) 1999-02-01
FI115398B (fi) 2005-04-29
DE59407302D1 (de) 1998-12-24

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